Tuning cesium–guanidinium in formamidinium tin triiodide perovskites with an ethylenediammonium additive for efficient and stable lead-free perovskite solar cells

Tosado, Gabriella A.; Zheng, Erjin; Yu, Qiuming

doi:10.1039/d0ma00520g

Cited by 22 publications

(16 citation statements)

References 47 publications

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“…The results also show a slight drop in the iodide concentration (I 3d, %) at 1−5% CsI. Tosado et al 36 and Hao et al 1 also reported about Sn 2+ oxidation in MASnI 3 , resulting in Sn 2+ and I − vacancies. As we know, the oxidation reaction of Sn 2+ to Sn 4+ produces two electrons (Sn 2+ ↔ Sn 4+ + 2e − ), and this reversible reaction is known as a self-doping process.…”

Section: ■ Methodsmentioning

confidence: 59%

“…As we know, the oxidation reaction of Sn 2+ to Sn 4+ produces two electrons (Sn 2+ ↔ Sn 4+ + 2e − ), and this reversible reaction is known as a self-doping process. 2,36 We suspect that Cs x FA 1−x SnI 3 can form in the Sn-enrichment condition because Cs + consumes electrons, which are produced from the Sn 2+ oxidation. Then, phase separation begins at 10% CsI, where the ratio of Sn 2+ −I increases again (Figure 3c and Table S1).…”

Section: ■ Methodsmentioning

confidence: 99%

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Phase Evolution in Lead-Free Cs-Doped FASnI₃ Hybrid Perovskites and Optical Properties

et al. 2021

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Tin halide perovskites are among the candidates having potential to substitute lead-based perovskites due to their environmentally benign components and potential medical usage. Nevertheless, the air stability remains a challenge due to Sn2+ oxidation. The recent developments have shown that adding SnF2 as an additive and A-site cation replacement by an inorganic element such as Cs+ can improve the film stability. However, exploring the structural change through A-site doping in Sn-based perovskites experimentally requires an in-depth investigation. Here, the phase evolution mechanism from the transformation of CsxFA1–x SnI3 to Cs2SnI6 via Cs2–x FA x SnI6 in the presence of the intermediate phase SnI2–(dmf) x due to Cs substitution in FASnI3 and the substitution’s influences on the optical properties were identified and investigated. Introducing a small amount of Cs+ (≤5% CsI) significantly promoted Sn2+ oxidation due to the anharmonic lattice dynamics. Later, at 10% CsI, self-doping was initiated, resulting in the coexistence of Sn2+/Sn4+. However, phase separation of Cs2SnI6 via Cs2–x FA x SnI6 occurred at contents greater than 10% CsI. Notably, the absorption coefficient was amplified along with the increasing Cs content (at 10% CsI, 6 times greater than that of FASnI3). The air stability was also enhanced as a result of Cs substitution. This work demonstrates the structural engineering of A-site cations in order to obtain various material properties for photovoltaic (PV) and non-PV applications.

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Section: ■ Methodsmentioning

confidence: 59%

Section: ■ Methodsmentioning

confidence: 99%

Phase Evolution in Lead-Free Cs-Doped FASnI₃ Hybrid Perovskites and Optical Properties

et al. 2021

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“…[169] Tosado et al researched the impact of A-site cation www.advancedsciencenews.com mixing of FA by CsGA together with EDAI 2 on the stability of pure Sn PSCs. [122] To establish hydrogen bonding and alleviate local strains, they added Cs + and GA + cations into FASnI 3 crystal structure. GA + in FASnI 3 minimizes phase segregation due to the many hydrogen bonding sites, practically a good alternative for stabilizing mixed Sn-based perovskites.…”

Section: Improvement Of Film Quality and Defects Reductionmentioning

confidence: 99%

Methylammonium and Bromide‐Free Tin‐Based Low Bandgap Perovskite Solar Cells

Imran

Rauf

Raza

et al. 2022

Advanced Energy Materials

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its volatility and reversible/irreversible decomposition reaction even at low temperature, MA is gradually avoided in the material designs. [9] At the same time, FA is more thermally stable than MA due to its stronger hydrogen bonding with PbX 6 octahedra and benign reversible decomposition reaction below 85 °C, and it is the primary cation in practically all current high-performance PSCs. [10,11] Also, FA has no irreversible (nonselective) back reaction. [12] At the same time, in order to approach the bandgap of 1.34 eV according to the Schottky-Queisser (S-Q) limit, from initially MAPbI 3 to double cation (MAFA or FACs), [10,13,14] triple cation (CsMAFA) based perovskites, [5] eventually to quadruple (CsRbMAFA) based perovskites, [4,[15][16][17] and recently FAPbI 3 are dominated ones. [18][19][20] FAPbI 3 has an ideal, narrow bandgap since FA remains the largest organic cation that fits into a 3D perovskite crystal structure. [21] The implicit or explicit goal of perovskite research is to obtain a black FA-based (stable phase) perovskite at room temperature. Avoiding yellow phase impurities encouraged the advancement of processing techniques and elaborate multication, multi-halide mixtures.It has been proved that the invasion of Br anion at the X site is effective for stabilizing the black phase FA-based and other perovskites. But it leads to an adverse blue-shift of the bandgap disproportionately. For example, there is a spanning of 700 meV persisting in MAPbI x Br 1-x from 2.28 eV (MAPbBr 3 ) to 1.58 eV (MAPbI 3 ). [22] Furthermore, from a stability perspective, introducing Br anion in iodide-based perovskites is unfavorable since Br/I mixtures will undergo severe anion segregation Lead halide-based perovskite solar cells (PSCs) are intriguing candidates for photovoltaic technology because of their high efficiency, low cost, and simple process advantages. Owing to lead toxicity, PSCs based on partially/fully substituted Pb with tin have attracted tremendous attention, which would enable the ideal bandgap to approach the Shockley-Queisser (S-Q) limit. Especially, methylammonium (MA), bromide-free, tin-based perovskites are striking, because of the intrinsic poor stability of MA and blue shift caused by the incorporation of Br − . The first section of this review emphasizes the motivation for studying single-junction MA, Br-free, and Sn-based perovskites. The film quality improvement strategies of Sn-based perovskites, including additive, composition, dimensional, and interface engineering toward high-efficiency devices are comprehensively overviewed. Moreover, strategies to improve stability, where shelf, thermal and operational stabilities of the devices are summarized. Finally, this review concludes with a discussion of actual limitations and future prospects for Sn-based PSCs.

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“…The stability of the devices was guaranteed over a long period (4000 h). The use of ethylenediammonium additive combined with Cs and GA doping of FASnI 3 induces passivation, which reduces defect density and allows fine control of film quality as well as stability 169 .…”

Section: Reducing Agentsmentioning

confidence: 99%

A Review of Three-Dimensional Tin Halide Perovskites as Solar Cell Materials

2022

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Thin film solar cell materials such as 3D metal halide perovskites are cheaper alternatives to silicon. Presently, the conversion efficiency of 3D lead halide perovskites is 25.5% ( 2021), which represents an increase of more than 550% since their discovery in 2009 (3.8%). Despite this remarkable progress, concerns about the toxicity of lead have sparked the quest for possible substitutes, in particular, 3D tin halide perovskites. This review covers the general properties of tin halide perovskites, synthesis and stability. It also identifies possible gaps and application beyond solar cells.

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Tuning cesium–guanidinium in formamidinium tin triiodide perovskites with an ethylenediammonium additive for efficient and stable lead-free perovskite solar cells

Abstract: Utilizing cation tuning and implementing divalent cation hollowing and passivation to achieve efficient and stable pure Sn-based perovskite solar cells.

Cited by 22 publications

References 47 publications

Phase Evolution in Lead-Free Cs-Doped FASnI₃ Hybrid Perovskites and Optical Properties

Phase Evolution in Lead-Free Cs-Doped FASnI₃ Hybrid Perovskites and Optical Properties

Methylammonium and Bromide‐Free Tin‐Based Low Bandgap Perovskite Solar Cells

A Review of Three-Dimensional Tin Halide Perovskites as Solar Cell Materials

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Tuning cesium–guanidinium in formamidinium tin triiodide perovskites with an ethylenediammonium additive for efficient and stable lead-free perovskite solar cells

Abstract: Utilizing cation tuning and implementing divalent cation hollowing and passivation to achieve efficient and stable pure Sn-based perovskite solar cells.

Cited by 22 publications

References 47 publications

Phase Evolution in Lead-Free Cs-Doped FASnI3 Hybrid Perovskites and Optical Properties

Phase Evolution in Lead-Free Cs-Doped FASnI3 Hybrid Perovskites and Optical Properties

Methylammonium and Bromide‐Free Tin‐Based Low Bandgap Perovskite Solar Cells

A Review of Three-Dimensional Tin Halide Perovskites as Solar Cell Materials

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Phase Evolution in Lead-Free Cs-Doped FASnI₃ Hybrid Perovskites and Optical Properties

Phase Evolution in Lead-Free Cs-Doped FASnI₃ Hybrid Perovskites and Optical Properties